The present invention relates to novel reactive colorants, to a process for their production and to their use.
The practice of dyeing using reactive dyes has recently led to higher demands being made on the quality of the dyeings and the profitability of the dyeing process. As a result, there is still a need for novel reactive dyes having improved properties, especially in respect of their application.
Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.
The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes having the qualities characterised above to a high degree. The novel dyes should especially be distinguished by high fixing yields and high fibre-dye binding stability, and it should also be possible for dye that is not fixed to the fibre to be washed off easily. The dyes should also yield dyeings having good allround properties, for example fastness to light and to wetting.
It has been shown that the problem posed is largely solved by the novel reactive dyes defined below.
The present invention accordingly relates to compounds of formula (1) 
wherein
K1 and K2 are each independently of the other the radical of a coupling component from the series benzene, naphthalene, 4-alkyl-6-hydroxypyridone-(2), 2,5-diamino-4-alkylpyridine, 1-arylpyrazolone-(5) and 1-aryl-5-aminopyrazole, at least one of the radicals K1 and K2 containing a fibre-reactive group,
with the proviso that
(i) the fibre-reactive group is not 2-(xcex2-sulfatoethylsulfonyl)ethylamino when K1 and K2 are phenyl substituted by a fibre-reactive group, and
(ii) the fibre-reactive group is not xcex2-sulfatoethylsulfonyl when K1 and K2 are N-(xcex2-sulfatoethyl)aniline substituted on the phenyl ring by a fibre-reactive group.
The radicals K1 and K2 may contain substituents customary in dyes.
From the series of substituents there may be mentioned by way of example: alkyl groups having from 1 to 12 carbon atoms, especially from 1 to 4 carbon atoms, such as methyl, ethyl, n- or iso-propyl, and n-, iso-, sec- or tert-butyl, alkoxy groups having from 1 to 8 carbon atoms, especially from 1 to 4 carbon atoms, such as methoxy, ethoxy, n- or iso-propoxy, and n-, iso-, sec- or tert-butoxy, C1-C4alkoxy substituted in the alkyl moiety, for example, by hydroxy, C1-C4alkoxy or by sulfato, such as 2-hydroxyethoxy, 3-hydroxy-propoxy, 2-sulfatoethoxy, 2-methoxyethoxy or 2-ethoxyethoxy, alkanoylamino groups having from 2 to 8 carbon atoms, especially C2-C4alkanoylamino groups, such as acetyl-amino or propionylamino, benzoylamino or C2-C4alkoxycarbonylamino groups, such as methoxycarbonylamino or ethoxycarbonylamino, amino, N-mono- or N,N-di-C1-C4-alkylamino unsubstituted or substituted in the alkyl moiety, for example, by hydroxy, sulfo, sulfato or by C1-C4alkoxy, such as methylamino, ethylamino, N,N-dimethyl- or N,N-diethyl-amino, sulfomethylamino, xcex2-hydroxyethylamino, N,N-di(2-hydroxyethylamino), N-xcex2-sulfato-ethylamino, phenylamino unsubstituted or substituted in the phenyl moiety by methyl, methoxy, halogen or by sulfo, Nxe2x80x94C1-C4alkyl-N-phenylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfo or by sulfato or unsubstituted or substituted in the phenyl moiety by methyl, methoxy, halogen or by sulfo, such as N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-xcex2-hydroxyethyl-N-phenylamino or N-xcex2-sulfoethyl-N-phenylamino, unsubstituted or sulfo-substituted naphthylamino, alkanoyl groups having from 2 to 8 carbon atoms, especially from 2 to 4 carbon atoms, such as acetyl or propionyl, benzoyl, alkoxy-carbonyl having from 1 to 4 carbon atoms in the alkoxy moiety, such as methoxycarbonyl or ethoxycarbonyl, alkylsulfonyl having from 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl, phenyl- or naphthyl-sulfonyl, trifluoromethyl, nitro, cyano, hydroxy, halogen, such as fluorine, chlorine or bromine, carbamoyl, Nxe2x80x94C1-C4alkylcarbamoyl, such as N-methyl-carbamoyl or N-ethylcarbamoyl, sulfamoyl, Nxe2x80x94C1-C4alkylsulfamoyl, such as N-methyl-sulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, N-(xcex2-hydroxyethyl)sulfamoyl, N,N-di(xcex2-hydroxyethyl)sulfamoyl, N-phenylsulfamoyl, ureido, carboxy, sulfomethyl, sulfo or sulfato, and fibre-reactive radicals. The alkyl radicals may additionally be interrupted by oxygen (xe2x80x94Oxe2x80x94) or by an amino group (xe2x80x94NHxe2x80x94, xe2x80x94N(C1-C4alkyl)-).
The term xe2x80x9csulfoxe2x80x9d here generally includes both the free acid xe2x80x94SO3H and any desired salt form, for example an alkali metal, alkaline earth metal or ammonium salt or the salt of an organic amine. Examples thereof include the sodium, potassium, lithium or ammonium salt or the salt of triethanolamine.
Preferably each of the radicals K1 and K2 in the compounds according to the invention contains at least one fibre-reactive group, and especially one fibre-reactive group. xe2x80x9cFibre-reactive radicalsxe2x80x9d are to be understood as meaning those that are capable of reacting with the hydroxy groups of cellulose, with the amino, carboxy, hydroxy and thiol groups in wool and silk, or with the amino and, where present, carboxy groups of synthetic polyamides, with the formation of covalent chemical bonds. The fibre-reactive radicals are generally bound to the dye radical directly or by way of a bridge member. Suitable fibre-reactive radicals include, for example, those containing at least one removable substituent on an aliphatic, aromatic or heterocyclic radical or wherein the mentioned radicals contain a radical suitable for reaction with the fibre material, such as, for example, a vinyl radical. A fibre-reactive radical present in K1 or K2 preferably corresponds to formula (2a), (2b), (2c), (2d) or (2e)
xe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2a),
xe2x80x94CONR2xe2x80x94(CH2)nxe2x80x94SO2xe2x80x94Yxe2x80x83xe2x80x83(2b),
xe2x80x94Nxe2x80x94COxe2x80x94CH(Hal)xe2x80x94CH2-Hal (2c),
xe2x80x83xe2x80x94NHxe2x80x94COxe2x80x94C(Hal)xe2x95x90CH2xe2x80x83xe2x80x83(2d) or

wherein
Hal is chlorine or bromine and
X is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl,
T independently thereof has a meaning given for X or is hydroxy, C1-C4alkoxy, phenoxy, C1-C4alkylthio, morpholino, amino unsubstituted or substituted by non-fibre-reactive radicals, or a fibre-reactive radical of formula (3a), (3b), (3c), (3d), (3e) or (3f) 
R1 and R1a are each independently of the other hydrogen or C1-C4alkyl,
R2 is hydrogen, C1-C4alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or by cyano, or a radical 
R3 is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C1-C4alkoxycarbonyl, C1-C4alkanoyloxy, carbamoyl or the group xe2x80x94SO2xe2x80x94Y,
alk and alk, are each independently of the other C1-C6alkylene,
arylene is a phenylene or naphthylene radical unsubstituted or substituted by sulfo, carboxy, C1-C4alkyl, C1-C4alkoxy or by halogen,
Y1 is a group xe2x80x94CH(Hal)xe2x80x94CH2xe2x80x94Hal or xe2x80x94C(Hal)xe2x95x90CH2 and Hal is chlorine or bromine,
Q is a radical xe2x80x94Oxe2x80x94 or xe2x80x94NR1xe2x80x94, wherein R1 is as defined above,
W is a group xe2x80x94SO2xe2x80x94NR2xe2x80x94, xe2x80x94CONR2xe2x80x94 or xe2x80x94NR2COxe2x80x94,
n is an integer from 1 to 6 and m is 0 or 1 and
Y is vinyl or a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U and U is a group removable under alkaline conditions.
As a leaving group U there come into consideration, for example, xe2x80x94Cl, xe2x80x94Br, xe2x80x94F, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OPO3H2, xe2x80x94OCOxe2x80x94C6H5, xe2x80x94OSO2xe2x80x94C1-C4alkyl or xe2x80x94OSO2xe2x80x94N(C1-C4alkyl)2. U is preferably a group of formula xe2x80x94Cl, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3,xe2x80x94OCOxe2x80x94C6H5 or xe2x80x94OPO3H2, especially xe2x80x94Cl or xe2x80x94OSO3H and more especially xe2x80x94OSO3H.
Examples of suitable radicals Y are accordingly vinyl, xcex2-bromo- or xcex2-chloroethyl, xcex2-acetoxy-ethyl, xcex2-benzoyloxyethyl, xcex2-phosphatoethyl, xcex2-sulfatoethyl and xcex2-thiosulfatoethyl. Y is preferably vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl and especially vinyl or xcex2-sulfatoethyl.
R1 and R1a are each independently of the other preferably hydrogen, methyl or ethyl and especially hydrogen.
R2 is preferably hydrogen or C1-C4alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl and especially hydrogen, methyl or ethyl. R2 is more especially hydrogen.
R3 is preferably hydrogen.
n is preferably the number 2, 3 or 4, especially the number 2 or 3 and more especially the number 2.
When T is amino unsubstituted or substituted by non-fibre-reactive radicals, it may be amino, Nxe2x80x94C1-C4alkylamino or N,N-di-C1-C4alkylamino, the alkyl being unsubstituted or substituted, for example, by sulfo, sulfato, hydroxy, carboxy or by phenyl, cyclohexylamino, Nxe2x80x94C1-C4alkyl-N-phenylamino or phenylamino or naphthylamino, the phenyl or naphthyl being unsubstituted or substituted, for example, by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, carboxy, sulfo or by halogen.
Examples of suitable non-fibre-reactive amino radicals T include amino, methylamino, ethylamino, xcex2-hydroxyethylamino, N,N-di-p-hydroxyethylamino, xcex2-sulfoethylamino, cyclohexylamino, morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenyl-amino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.
As non-fibre-reactive radical, T is preferably C1-C4alkoxy, C1-C4alkylthio, hydroxy, amino, Nxe2x80x94C1-C4alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo, morpholino, phenylamino or Nxe2x80x94C1-C4alkyl-N-phenylamino wherein the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, acetylamino, methyl or by methoxy.
Especially preferred non-fibre-reactive radicals T are amino, N-methylamino, N-ethylamino, morpholino, phenylamino, 2-, 3- or 4-sulfophenylamino or Nxe2x80x94C1-C4alkyl-N-phenylamino.
X is preferably halogen, e.g. fluorine, chlorine or bromine and especially chlorine or fluorine.
Hal is preferably bromine.
alk and alk, are each independently of the other, for example, a methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or a branched isomer thereof.
alk and alk, are each independently of the other preferably a C1-C4alkylene radical and especially an ethylene radical or a propylene radical.
arylene is preferably an unsubtituted or, for example, sulfo-, methyl-, methoxy- or carboxy-substituted 1,3- or 1,4-phenylene radical and especially an unsubstituted 1,3- or 1,4-phenylene radical.
Q is preferably xe2x80x94NHxe2x80x94 or xe2x80x94Qxe2x80x94 and especially xe2x80x94Oxe2x80x94.
W is preferably a group of formula xe2x80x94CONHxe2x80x94 or xe2x80x94NHCOxe2x80x94, especially a group of formula xe2x80x94CONHxe2x80x94.
m is preferably 0.
Preferred as reactive radicals of formulae (3a) to (3f) are those wherein W is a group of formula xe2x80x94CONHxe2x80x94, R1, R2 and R3 are in each case hydrogen, Q is the radical xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94, alk and alk, are each independently of the other ethylene or propylene, arylene is unsubstituted or methyl-, methoxy-, carboxy- or sulfo-substituted phenylene, Y is vinyl or xcex2-sulfatoethyl, Y1 is xe2x80x94CHBrxe2x80x94CH2Br or xe2x80x94CBrxe2x95x90CH2 and m is 0.
A reactive radical present in K1 or K2 is preferably a radical of the formula (2a), (2b), (2c), (2d) or (2e) given above wherein Hal is bromine, R2 is hydrogen, n is the number 2 or 3, X is halogen, T is C1-C4alkoxy, C1-C4alkylthio, hydroxy, amino, Nxe2x80x94C1-C4alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo, morpholino, phenylamino or Nxe2x80x94C1-C4alkyl-N-phenylamino wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato and the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, acetylamino, methyl or by methoxy, or a fibre-reactive radical of formula (3cxe2x80x2) or (3dxe2x80x2) 
and Y is vinyl or xcex2-sulfatoethyl.
Especially preferably the radicals K1 and K2 each independently of the other contain a radical of formula (2a), (2b), (2c) or (2d) given above, preferably (2a) or (2b) and especially (2a), wherein R2, Y and n each have the definitions and preferred meanings given above. K1 and K2 are each independently of the other, for example, a radical of formula 
wherein
(R4)0-3 denotes from 0 to 3 identical or different radicals selected from the group C1-C4alkyl, C1-C4alkoxy, C1-C4alkoxy substituted in the alkyl moiety by hydroxy, C1-C4alkoxy or by sulfato, halogen, carboxy, hydroxy, amino, N-mono- or N,N-di-C1-C2alkylamino, C2-C4-alkanoylamino, ureido, sulfo, C1-C4alkylsulfonyloxy, C1-C4alkylsulfonylamino and a reactive radical of formula (2e) given above;
(R4a)0-2 denotes from 0 to 2 identical or different radicals selected from the group C1-C4-alkyl, C1-C4alkoxy, phenoxy, halogen, sulfo and hydroxy;
R5 is hydrogen or C1-C4alkyl;
R5a independently thereof has a meaning given for R5 or is C2-C4alkanoyl, C1-C4hydroxy-alkyl, C1-C4sulfatoalkyl, C1-C4alkoxyalkyl or unsubstituted or methyl-, methoxy-, chloro- or sulfo-substituted phenyl;
R6 is hydrogen, C1-C4alkyl or phenyl;
(R7)0-2 denotes from 0 to 2 identical or different substituents selected from the group hydroxy and the fibre-reactive radical of formula (2a) given above;
R8 is hydrogen or C1-C4alkyl unsubstituted or substituted by hydroxy, C1-C4alkoxy, sulfato, sulfo, halogen or by cyano;
R9 independently thereof has a meaning given for R8 or is C2-C4alkanoyl or benzoyl, or wherein xe2x80x94NR8R9 is a fibre-reactive radical of formula (2e) given above;
R10 and R10a are each independently of the other carbamoyl, sulfomethyl or cyano;
R11 is hydrogen or C1-C4alkyl unsubstituted or substituted by a radical of formula (2e) given above;
R12 and R13 are each independently of the other hydrogen or C1-C12alkyl unsubstituted or substituted by hydroxy, C1-C4alkoxy, phenoxy, sulfato, sulfo, carboxy, amino or by N-mono-or N,N-di-C1-C4-alkylamino (the alkyl moiety or moieties of which may itself or themselves be substituted by hydroxy, C1-C4alkoxy, phenoxy, sulfato, sulfo, carboxy or by a fibre-reactive radical of formula (2e) given above) and/or uninterrupted or, with the exception of methyl, interrupted by xe2x80x94Oxe2x80x94;
R14 is methyl or carboxy;
R15 is hydroxy or amino;
(R16)0-3 denotes from 0 to 3 identical or different radicals selected from the group sulfo, halogen, hydroxy, C1-C4alkoxy and C1-C4alkyl;
(R17)0-2 denotes from 0 to 2 identical or different radicals selected from the group C1-C4-alkyl, C1-C4alkoxy, C1-C4alkoxy substituted in the alkyl moiety by hydroxy, C1-C4alkoxy or by sulfato, C2-C4alkanoylamino, ureido, halogen and sulfo;
K is a radical of formula (4a), (4b), (4c), (4d), (4e), (4f), (4g) or (4h) or (4j), (4k) or (4l) given above and is preferably a radical of formula (4e);
D is a phenyl or 1- or 2-naphthyl radical containing from 1 to 3 identical or different radicals from the group sulfo, C1-C4alkyl, C1-C4alkoxy, halogen and a fibre-reactive radical of formula (2a), (2b), (2c) or (2d);
Da is the radical of a monoazo or disazo chromophore; and each of X and Y has the meanings given above.
The following preferred meanings apply for the variables given in formulae (4a) to (4l):
(R4)0-3 preferably denotes from 0 to 3 identical or different radicals selected from the group methyl, methoxy, ethoxy substituted in the alkyl moiety by hydroxy, methoxy, ethoxy or by sulfato, chlorine, hydroxy, amino, N-mono- or N,N-di-C1-C2alkylamino, acetylamino, propionylamino, sulfo, and a reactive radical of formula (2e) given above, wherein X is halogen, R1a is hydrogen and T is amino or morpholino unsubstituted or substituted by non-fibre-reactive radicals;
(R4a)0-2 preferably denotes from 0 to 2 identical or different radicals selected from the group methyl, methoxy, phenoxy, chlorine, sulfo and hydroxy;
R5 is hydrogen, methyl or ethyl;
R5a independently thereof has a meaning given for R5 or is acetyl, propionyl, 2-hydroxyethyl or 2-sulfatoethyl;
R6 is preferably hydrogen;
R8 is preferably hydrogen and R9 is preferably acetyl, propionyl or benzoyl, or xe2x80x94NR8R9 is a fibre-reactive radical of formula (2e) given above;
R10 is preferably carbamoyl or sulfomethyl;
R10a is preferably cyano or carbamoyl;
R11 is preferably methyl or ethyl;
R12 is preferably hydrogen or C1-C6alkyl unsubstituted or substituted by hydroxy, methoxy, ethoxy, sulfato or by sulfo;
R13 independently thereof preferably has a meaning given for R12 or is a radical of formula (2e) given above;
R12 and R13 are each independently of the other especially hydrogen or C1-C6-alkyl unsubstituted or substituted by hydroxy, sulfo or by sulfato;
R15 is preferably hydroxy;
(R16)0-3 preferably denotes from 0 to 3 identical or different radicals selected from the group sulfo, methyl, methoxy, hydroxy and chlorine;
(R17)0-2 preferably denotes from 0 to 2 identical or different radicals selected from the group methyl, methoxy, C1-C2alkoxy substituted in the alkyl moiety by hydroxy or by sulfato, acetylamino, propionylamino and sulfo;
D is preferably a phenyl or 1- or 2-naphthyl radical containing from 1 to 3 identical or different radicals from the group sulfo, methyl, methoxy, chlorine and a fibre-reactive radical of formula (2a), (2b), (2c) or (2d); and
Da is preferably the radical of a monoazo or disazo chromophore having diazo components and coupling components from the benzene or naphthalene series that are substituted by one or more substituents from the group sulfo, methyl, methoxy, chlorine, amino, hydroxy, acetylamino, propionylamino, benzoylamino, ureido, 2-hydroxyethoxy, 2-sulfatoethoxy and a fibre-reactive radical of formula (2e). Da in formula (4l) is especially a radical of formula (5a) or (5b)
xe2x80x94Da*xe2x80x94Nxe2x95x90Nxe2x80x94Ka (xe2x80x94Nxe2x95x90Nxe2x80x94Da**)0-1xe2x80x83xe2x80x83(5a) or
xe2x80x94Kaxe2x80x94Nxe2x95x90Nxe2x80x94(Maxe2x80x94Nxe2x95x90Nxe2x80x94)0.1Da*xe2x80x83xe2x80x83(5b),
wherein Da* is an unsubstituted or sulfo-substituted phenylene radical, Da** is phenyl or naphthyl unsubstituted or substituted by sulfo or by a radical of formula (2a) given above, Ka is the radical of a coupling component from the aminonaphtholsulfonic acid series, e.g. the radical of H , K, I or xcex3 acid unsubstituted or substituted on the amino group by acetyl, propionyl, benzoyl or by a fibre-reactive radical of formula (2e) given above, and Ma is phenylene unsubstituted or substituted by sulfo, methyl, methoxy, acetylamino, ureido, 2-hydroxyethoxy or by 2-sulfatoethoxy.
K1 and K2 are each independently of the other preferably a radical of formula (4cxe2x80x2), (4cxe2x80x3), (4dxe2x80x2), (4exe2x80x2), (4fxe2x80x2), (4gxe2x80x2), (4hxe2x80x2), (4ixe2x80x2), (4jxe2x80x2) or (4kxe2x80x2) 
wherein
R9 is acetyl, benzoyl or a radical of formula (2exe2x80x2) 
xe2x80x83wherein
the definitions and preferred meanings given above for each of X and T apply,
R18 is hydrogen, hydroxy or sulfato,
R19 independently thereof has a meaning given for R18 or is a radical of formula (2e),
R20 and R21 are each independently of the other hydrogen, methyl, methoxy, 2-hydroxy-ethoxy, 2-sulfatoethoxy, acetylamino, propionylamino, ureido or sulfo,
(R22)0-3 denotes from 0 to 3 identical or different radicals selected from the group sulfo, chlorine, C1-C4alkyl and C1-C4alkoxy,
(Z)0-1, where present, denotes a radical of formula (2a), (2b), (2c) or (2d) and the definitions and preferred meanings given above for Y apply.
The radicals K1 and K2 are each independently of the other especially a radical of formula (4exe2x80x2), (4jxe2x80x2) or (4kxe2x80x2) given above and more especially of formula (4jxe2x80x2) or (4kxe2x80x2).
The radicals K1 and K2 may be different or, preferably, identical.
In a preferred embodiment of the present invention, the compounds of formula (1) are compounds of formula (1a) 
wherein
D1 is a radical of formula (6a) 
D2 is a radical of formula (6b) 
(R22a)0-2 and (R22b)0.2 each independently of the other denote from 0 to 2 identical or different substituents selected from the group sulfo, chlorine, C1-C4alkyl and C1-C4alkoxy,
of the radicals G1 and G2 one is hydroxy and the other is amino,
of the radicals G3 and G4 one is hydroxy and the other is amino,
p, q, r and s are each independently of the others 0 or 1,
the sum of p and q being the number 1 or 2, especially 2,
the sum of r and s being the number 1 or 2, especially 2, and
Za and Zb are each independently of the other a radical of formula (2a), (2b), (2c) or (2d) given above.
In a special embodiment of the present invention, the radicals D1 and D2 in the compounds of formula (1a) according to the invention have identical meanings.
In an especially preferred embodiment of the present invention, the compounds of formula (1a) are compounds of formula (1b) or (1c) 
wherein
D1 and D2 are each independently of the other a radical of formula (6c), (6d), (6e) or (6f) 
xe2x80x83wherein
(R22c)0-2 denotes from 0 to 2 identical or different substituents selected from the group sulfo, methyl and methoxy,
Zc is xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino,
n is the number 2, 3 or 4 and
Y is vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl, especially vinyl or xcex2-sulfatoethyl.
Preference is given to compounds of formula (1b) or (1c), wherein
D1 and D2 are radicals of formula (6c) wherein
(R22c)0-2 denotes from 0 to 2 identical or different substituents selected from the group methyl and methoxy, and
Y is vinyl or xcex2-sulfatoethyl.
The present invention relates also to a process for the preparation of compounds of formula (1), wherein
approximately 1 molar equivalent of the compound of formula 
xe2x80x83is tetraazotised in customary manner with a nitrite, e.g. sodium nitrite, in an acid medium, e.g. hydrochloric acid, and the tetraazotised compound is coupled with approximately 1 molar equivalent of a coupling component of formula
K1xe2x80x94Hxe2x80x83xe2x80x83(8) and
xe2x80x83with approximately 1 molar equivalent of a coupling component of formula
K2xe2x80x94Hxe2x80x83xe2x80x83(9)
xe2x80x83in an acid, neutral or alkaline medium, wherein the definitions and preferred meanings given above for each of K1 and K2 apply.
When K1xe2x80x94H and K2xe2x80x94H are identical coupling components, it is advantageous to react approximately 1 molar equivalent of the tetraazotised compound of formula (7) with approximately 2 molar equivalents of a compound of formula (8).
The synthesis of the compounds of formula (1) can also be carried out by first coupling the tetraazotised compound of formula (7) with a precursor of K1xe2x80x94H or K2xe2x80x94H and then converting the resulting disazo compound into the final compound, for example by coupling with a further diazotised diazo component.
The preferred compounds of formula (1b) can advantageously be prepared, for example, according to process variant xe2x80x9cAxe2x80x9d, by:
(i) coupling approximately 1 molar equivalent of a diazotised compound of formula (10a)
D1xe2x80x94NH2xe2x80x83xe2x80x83(10a),
xe2x80x83wherein D1 is as defined above, with approximately 1 molar equivalent of a coupling component of formula (11) 
(ii) independently thereof coupling approximately 1 molar equivalent of a diazotised compound of formula (10b)
D2xe2x80x94NH2xe2x80x83xe2x80x8310b),
xe2x80x83wherein D2 is as defined above, with approximately 1 molar equivalent of a coupling component of formula (11), and
(iii) coupling approximately 1 molar equivalent of each of the monoazo compounds obtained according to (i) and (ii) with approximately 1 molar equivalent of a tetraazotised compound of formula (7).
When D1xe2x80x94NH2 and D2xe2x80x94NH2 in process variant xe2x80x9cAxe2x80x9d are identical compounds, it is advantageous to react approximately 2 molar equivalents of a diazotised compound of formula (10a) with approximately 2 molar equivalents of a compound of formula (11) and then to couple the resulting monoazo compound with approximately 1 molar equivalent of a tetraazotised compound of formula (7).
When D1xe2x80x94NH2 and D2xe2x80x94NH2 in process variant xe2x80x9cAxe2x80x9d are not identical compounds, process steps (i) and (ii) can be combined by diazotising approximately 2 molar equivalents of a mixture of amines D1xe2x80x94NH2 and D2xe2x80x94NH2, e.g. a 1:1 molar mixture, and coupling with approximately 2 molar equivalents of a coupling component of formula (11) and then proceeding further according to (iii).
The preferred compounds of formula (1 c) can advantageously be prepared, for example, according to process variant xe2x80x9cBxe2x80x9d, by:
(i) coupling approximately 0.5 molar equivalent of a previously tetraazotised compound of formula (7) with approximately 1 molar equivalent of a compound of formula (11) given above, and then
(ii) coupling the resulting disazo compound with approximately 1 molar equivalent of a diazotised compound of formula (10a) given above when D1xe2x80x94NH2 and D2xe2x80x94NH2 are identical compounds, or with, for example, a 1:1 molar mixture of approximately 1 molar equivalent of the diazotised compounds of formulae (10a) and (10b) when D1xe2x80x94NH2 and D2xe2x80x94NH2 are not identical compounds.
In the process variants xe2x80x9cAxe2x80x9d and xe2x80x9cBxe2x80x9d described above, the first coupling (A(i) and A(ii) or B(i)) takes place in an acid medium and the second coupling (A(iii) and B(ii)) takes place at a higher pH value in a weakly acid, neutral or weakly alkaline medium.
When D1xe2x80x94NH2 and D2xe2x80x94NH2 in the process variants xe2x80x9cAxe2x80x9d and xe2x80x9cBxe2x80x9d described above are not identical compounds, mixtures are obtained that also comprise, in addition to the compounds of formulae (1b) and (1c), which are asymmetric with respect to the radicals D1 and D2, the corresponding symmetric compounds of formulae 
In formulae (1b*), (1b**), (1c*) and (1c**), the definitions and preferred meanings given above for D1 and D2 apply. The present invention accordingly relates also to dye mixtures comprising a compound of formula (1b*) together with at least one compound of formulae (1b*) and (1b**), especially one compound of each of formulae (1b*), (1b*) and (1b**), and to dye mixtures comprising a compound of formula (1c) together with at least one compound of formulae (1c*) and (1c**), especially one compound of each of formulae (1c), (1c*) and (1c**).
The ratio of dyes of formulae (1b), (1b*) and (1b**) or (1c), (1c*) and (1c**) in the mixture in question can vary within wide ranges and will depend upon the ratio of amines D1xe2x80x94NH2 and D2xe2x80x94NH2 used according to A(i) and A(ii) or B(ii).
The above dye mixtures contain, for example, from 5 to 95% by weight, especially from 10 to 90% by weight, and preferably from 20 to 80% by weight, of a dye of formula (1b*) or (1c), based on the total amount of the dyes of formulae (1b*), (1b*) and (1b**) or (1c), (1c*) and (1c**) in the mixture in question.
If, in the above processes for the preparation of compounds of formulae (1b) and (1c), there is used, instead of a molar equivalent of a compound of formula (11), 1 molar equivalent of a mixture of two different compounds of formula (11), e.g. approximately 0.5 molar equivalent of an aminonaphtholdisulfonic acid KK1 and approximately 0.5 molar equivalent of an aminonaphtholdisulfonic acid KK2, there are then obtained mixtures of compounds that are symmetric and asymmetric with respect to the aminonaphtholdisulfonic acids KK1 and KK2.
The present invention accordingly relates also to dye mixtures comprising at least one compound of formulae (12a) and (12b) 
together with at least one compound of formulae (12c) and (12d) 
especially one compound of each of formulae (12a), (12b), (12c) and (12d), wherein the definitions and preferred meanings given above for the radicals D1 and D2 apply, and KK1 is preferably 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H acid) and KK2 is preferably 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid (K acid).
The ratio of dyes of formulae (12a), (12b), (12c) and (12d) in the mixtures can vary within wide ranges and will depend upon the ratio of aminonaphtholdisulfonic acids KK1 and KK2 used according to A(i) and A(ii) or B(i).
The above dye mixtures contain, for example, from 5 to 95% by weight, especially from 10 to 90% by weight, and preferably from 20 to 80% by weight of dyes of formulae (12a) and (12b), based on the total amount of the dyes of formulae (12a), (12b), (12c) and (12d).
The compounds of formulae (7), (8), (9), (10a), (10b) and (11) are known or can be obtained in a manner known per se.
The reactive dyes according to the invention and the mixtures of reactive dyes according to the invention are fibre-reactive, that is to say they are capable of reacting with the hydroxyl groups of cellulose or with the reactive centres of natural and synthetic polyamides, with the formation of covalent chemical bonds.
The reactive dyes and mixtures of reactive dyes according to the invention are suitable for dyeing and printing a wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials. Examples include silk, leather, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic fibre materials. Such fibre materials are, for example, natural cellulose fibre, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The reactive dyes according to the invention and the mixtures of reactive dyes according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres contained in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.
The reactive dyes and mixtures of reactive dyes according to the invention can be applied to the fibre material and fixed to the fibre in a number of ways, especially in the form of aqueous dye solutions or dye print pastes. They are suitable for the exhaust process and also for dyeing using the pad-dyeing process, can be used at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very small. The dyes and dye mixtures according to the invention are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics containing wool.
The dyeings and prints produced on cellulose fibre materials using the dyes and dye mixtures according to the invention have a high tinctorial strength and a high fibre-dye binding stability in both acidic and alkaline ranges, and they also have good fastness to light and very good wet-fastness properties, such as fastness to washing, water, seawater, crossdyeing and to perspiration, as well as good fastness to pleating, to pressing, to rubbing, and especially to chlorine.